Hydrochloric Acid → 3-chloro-4-{(E)-2-[5-(4-fluorophenyl)-1-methyl-1H-pyrazol-3-yl]vinyl}bicyclo[4.2.1]non-3-en-9-one

HRID 271304ノート

反応式

HRID 271304 の反応式
Cl.[Cl:2][C:3]1[CH2:10][CH:9]2[C:11]3(OCC[O:12]3)[CH:6]([CH2:7][CH2:8]2)[CH2:5][C:4]=1/[CH:16]=[CH:17]/[C:18]1[CH:22]=[C:21]([C:23]2[CH:28]=[CH:27][C:26]([F:29])=[CH:25][CH:24]=2)[N:20]([CH3:30])[N:19]=1.C(=O)([O-])O.[Na+]>C1COCC1>[Cl:2][C:3]1[CH2:10][CH:9]2[C:11](=[O:12])[CH:6]([CH2:5][C:4]=1/[CH:16]=[CH:17]/[C:18]1[CH:22]=[C:21]([C:23]3[CH:24]=[CH:25][C:26]([F:29])=[CH:27][CH:28]=3)[N:20]([CH3:30])[N:19]=1)[CH2:7][CH2:8]2

参加物

5

反応物 3

HCID 313Hydrochloric AcidHCID 516892Sodium BicarbonateHCID 693065173-{(E)-2-[4-chlorospiro[bicyclo[4.2.1]non-3-ene-9,2'-[1,3]dioxolan]-3-yl]vinyl}-5-(4-fluorophenyl)-1-methyl-1H-pyrazole

生成物 1

HCID 693100833-chloro-4-{(E)-2-[5-(4-fluorophenyl)-1-methyl-1H-pyrazol-3-yl]vinyl}bicyclo[4.2.1]non-3-en-9-one収率 94%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

実験手順

A mixture of 2N hydrochloric acid (100 ml) and the product of Step 2 (18.0 g, 43 mmol) in THF (100 ml) was stirred at 60° C. for 2 hrs. The reaction mixture was basified with saturated sodium hydrogen carbonate and then extracted with ethyl acetate (3×200 ml). The organic extract was washed with brine, dried over MgSO4 and concentrated in vacuo. The residue was purified by flash chromatography eluting with ethylacetate: hexane (1:1) to afford 3-chloro-4-{(E)-2-[5-(4-fluorophenyl)-1-methyl-1H-pyrazol-3-yl]vinyl}bicyclo[4.2.1]non-3-en-9-one (14.96 g, 94%). δH (400 MHz, CDCl3) 1.59-1.71 (2H, m), 1.76-1.83 (1H, m), 2.02-2.10 (2H, m), 2.38-2.51 (2H, m), 2.58-2.62 (1H, m), 2.87-2.90 (1H, m), 2.96-3.01 (1H, m), 3.84 (3H, s), 6.49 (1H, s), 6.64 (1H, d, J 16.5), 7.14-7.18 (2H, m), 7.38-7.42 (2H, m), 7.54 (1H, d, J 16.5).

後処理

  1. extractionextracted with ethyl acetate (3×200 ml)
  2. extractionThe organic extract
  3. washwas washed with brine
  4. dry with materialdried over MgSO4
  5. concentrationconcentrated in vacuo
  6. customThe residue was purified by flash chromatography
  7. washeluting with ethylacetate: hexane (1:1)

出典と根拠

ORDレコード
ord-4b94b48118254152a5fcdac3e3262050
出典データセット
uspto-grants-2008_11
特許番号
US07452899B2

反応ノート

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